Polyvinyl chloride and alkyl tin mercaptoalcohol monocarboxylic acid esters



United States Patent POLYVINYL CHLORIDE AND ALKYL TIN MER- .SSATPI'JIQSALCOHOL MONOCARBOXYLIC ACID William E. Leistner, Brooklyn, Richmond Hill,

Laboratory, Inc.,

and Arthur C. Hecker, N. Y., assignors to Argus Chemical a corporation of New York No Drawing. Application July 21, 1954 Serial No. 444,902

6 Claims. (Cl. 260-45.75)

wherein R stands for a radical selected from the group consisting of alkyl, aryl, oxyalkyl and oxyaryl, the furfuryl and tetrahydrofurfuryl radicals, X for the radical of an ester of a mercapto alcohol having from 2 to 4 carbon atoms, and having its sulfur atom linked to Sn, and n for an integral number from 1 to 3.

Examples for R are alkyls, such as methyl, ethyl, butyl, octyl, dodecyl, and octadecyl; .aryls, such as phenyl, tolyl, or xylyl; oxyalkyl' and oxyaryl, such as C H O, t s 8 17 s o s 4( s) s s( 3)2 and the furfuryl and tetrahydrofurfuryl groups.

Examples for X are the radicals of esters of mercapto alcohols, such as mercapto ethanol, HS.CH .CH .OH; mercapto butanol, HS.CH .CH .CH .CH OH; or monothioglycerin, HS.CH .CHOH.CH OH, with aliphatic acids or cycloaliphatic acids containing from 6 to 12 carbon atoms. Taking as specific examples the butyl-tin-rnercapto ethanol lauric acid esters, the product may have the following formulas:

The novel tin compounds used according to our invention are oily liquids of high viscosity, whose composition has in each case been ascertained by analysis.

They are soluble in many organic solvents, for instance in ether, benzene, toluene, chloroform, carbontetrachlon'de, etc.

A general method to prepare these compounds is first to prepare the desired ester of the mercapto alcohol chosen, and subsequently to react the ester with an organic tin halide, organic tin oxide, or a stannonic acid,-

.. ice

Preparation of tin derivatives:

Example 1.--The preparation of dibutyl-tin (Ii-mercapto ethanol trimethyl hexanoic acid ester One mol of mercapto ethanol, one mol trimethylhexanoic acid, and 200 cc. benzene, to which 0.3 gram p toluene sulfonic acid were added, are refluxed and 18 cc. water eliminated by azeotropic distillation.

Subsequently, V2 mol of dibutyl tin oxide is added, refluxing being continued until the theoretical amount of water has distilled off. Slight impurities are filtered oil and the benzene is distilled off. The residue is a very viscous liquid of a slightly yellowish color. It is soluble in ether, chloroform, carbontetrachloride, benzene, toluene, xylene, and other organic solvents.

Analysis Sn 8 Cale. values.. 17. 6 9. 6 Found values 17. 4 9. 7

The final product is similar in appearance and properties to the product obtained according to Example 1.

Analysis Sn S Oalc. values 16. 3 8. 9 Found values 16. 0 8.

Example 3.Preparati0n of dibutyl tin dir'nercapto ethanol lauric acid ester The procedure is similar to the one described in Example 1, except that instead of one mol trimethylhexanoic acid one mol lauric acid is reacted with the alcohol.

The final product is similar in appearance and properties to the material obtained according to Example 1.

Analysis Sn Cale. values 8. 5 8. 7

15. Found values 15.

Example 4.Preparati0n of dibutyl tin dimercapto ethanol tetrahydroabietic acid ester 1.2 mols of commercial tetrahydroabietic acid, one mol of mercapto ethanol, and 200 cc. benzene, to which 0.3 g. p-toluene sulfonic acid were added, are refluxed until 18 cc. water are eliminated by azeotropic distillation.

To this solution, 0.9 mol of dibutyl tin oxide is added and refluxed for one hour. In this case the amountfot' water which separates out is about 20% less than the calculated amount. The reaction product is filtered and the benzene stripped off the solution.

The residue is in appearance and properties similar to the material obtained according to Example 1.

Example, imflfiparazion .of. tributyl. tin monothioglycerin. dilauryl ester (04KB) Sn--(S.CHa-CHi.0Hs.O.C 0.011H23) (LC O. Cu 2a One mol monothioglycerin, t'wo mols lauric acid, and 400: cc. benzene, to. which 0.5 g. p-toluiene sulfonic acid were added, are. refluxed until, 36" cc. water have been eliminated by. azeotropic distillation.

To this solution, one mol tributyl tin monochloride is added and refluxed for onehour. The reaction product is;filte'red off and=washedwith water to eliminate the HCl formed inthereaction. Then the benzene isdriven off;

The residue is in appearance and properties similar to the material obtained according to Example 1.

Analysis Sn S Vnlues-calc' 15; 5 4. 2 Values found v 15. 2 4.

Example 6;.Preparati0n ofisopropyl-tin trismercapto ethanol trimetlzylhexanoic acid ester (C3H 1) S11 S-CHghCHgOCOCaHm) 3 Analysis Sn S Cale. values 1i. 5 11.8 Found values 14. 3 11. 9

Thenovel compounds made according to the methods described above may be used for various purposes. They are excellent stabilizers for chlorinated and other high molecular weight halogenated material and will, in the following, be described for that purpose.

The amount by weight of these compounds can be from 0.1 to

Example 7 100 parts of Vinylite VYNW (vinyl chloride and acetate copolymer 50 parts dioctyl phthalate, and 2 parts of the product of Example 1 as stabilizer are mixed by turnbling for a period of one hour. The whole mass is then transferredto a Banbury mixer and fused for 10 min. at a temperature of approximately 300 F. It is then dropped and transferred to a warm-up mill, whose roll temperature is likewise maintained at. 300 F. The material is then fed as needed to a 3 or 4 roll calender. The roll temperatures of the calender range'from 280-350 F. The vinyl compound is calendered into a film at 0.004 inch or any other desirable gage.

Example 8 A comparison test was made in which chlorinated paraffin was heated over a period of time, without any addition on the one hand, and with addition of a stabilizer made according to the invention on the other hand.

In this test, a nitrogen current was passed through chlorinated paraffin containing 40% chlorine, at a temperature of 150 F. for 12 hours. During the test, the paraffin lost 10% chlorine.

The same chlorinated paraflin, to which 3% of the product obtained in Example 3 were added, was treated in a similar manner and showed a loss of only 1% chlor-ine after 12 hours;

Exampl 9..

In a manner similar to the one described in Example 8, a comparison test was made with chlorinated paraflin, with and without addition of a stabilizer. The stabilizer used in this case was the one produced according to Example 4, of which 2% were added.

As compared to a loss of 10% chlorine when heated for 12 hoursto 150' F. without addition of. a stabilizer,.the chlorine IQss'in-the test with. the stabilizer only amounted to 1.5 24

Example 10 The following procedure is used to advantage in making a finished solution of the resin. We use parts of Vinylite VYNW- (vinyl chloride and acetate copolymer), along with 40 parts, of tricresylphosphate. This is weighed into a dry blender; 1 part of stabilizer (made as described in Examplel) is then added. The whole mass is agitated by tumbling for 30 minutes and then transferred. to a Z-rollmill. whose roll temperatures areabout 2400" E. The; mass is fluidized on the mill and then sheeted into strips whichare added to a mixture-consisting of 3 parts oflmethyl ethyl ketone and 1 part of toluene in a conventional mixer. The compound is agitated at room temperature in the mixer until complete solutionresults. The: proportion of. solvent used will vary. with the concentration of. solution desired, as, for instance, from 500 to 3,000 parts of solvent to 100 partsof the vinyl chloride resinused.

Example 11 In. making an extrudedproduct, the following is a.pre ierred procedure. We use 100parts of Geon 101 weighed into a dry blender along with 40 parts of dioctyl sebacate plasticizer and 2 parts of the stabilizer made according to Example 3; 5' partsof titanium dioxide is added as filler. Color is alsoadded. The whole mass is then tumbled for aperiod of about 1 hour and is then transferred to a Banbury mixer whose temperature is at approximately 300 F., for fusion. The mass is then dropped and transferred to a warm-up 'mill. Strips are taken off and fed into the hopper of an extruder and the compound is extruded in the form of a solid round rod whose diameter is approximately inch. The rod of compound is cooled and sliced to form. small pellets. These pellets are thenused for the extrusion of vinyl strips or sheets or to cover copper wire for insulation purposes.

In a similar manner to the one described in Examples 7 to 11, any. one of the tin compounds prepared'according to Examples 1 to 6 can be used as stabilizers for chlorinecontaining polyvinyl resins or chlorinated parafiin.

What we claim is:

l. A stabilized chlorine-containing resin. selected from the group consisting of polyvinyl chloride and a copolymer of vinyl chloride and-vinyl acetatewhich comprises from 0.1 to 10 percent. byweight of a compoundcorre wherein R standsfor an alkyl radical, X for a radical of anester of amercapto alcohol havingfrom 2-.4 carbon atoms withan acidselected from the group consisting of a saturated monobasic aliphatic acid containing from 6-12. carbon atoms and tetrahydroabietic acid, and n for an integral number fro-m 1-3, and wherein the S atom of the mercapto alcohol is directly'linked to tin.

2. A stabilized chlorine-containing resinous composition selected from the group consisting of polyvinyl chlorideand a copolymer of vinyl chloride and vinyl acetate containing 0.1% to 10% by weight of-a product consisting of. dibutyl tin dimercaptoethanol trimethylhexanoic acid ester.

3. A stabilized chlorine-containing resinous compositionselecte'd: from the-group consisting of polyvinyl chloride and a copolymer of vinyl chloride and vinyl acetateing of dibutyl tin dimercaptobutanol tn'methylhexanoic acid ester.

4. A stabilized chlorine-containing resinous composition selected from the group consisting of polyvinyl chloride and a copolymer of vinyl chloride and vinyl acetate containing 0.1% to 10% by weight of a product consisting of dibutyl tin dimercaptoethanol lauric acid ester.

5. A stabilized chlorine-containing resinous composition selected from the group consisting of polyvinyl chloride and a copolymer of vinyl chloride and vinyl acetate containing 0.1% to 10% by weight of a product consisting of tributyl tin monothioglycerin dilauryl ester.

acid ester.

References Cited in the file of this patent UNITED STATES PATENTS 2,648,650 Weinberg et al Aug. 11, 1953 

1. A STABILIZED CHLORINE-CONTAINING RESIN SELECTED FROM THE GROUP CONSISTING OF POLYVINYL CHLORIDE AND A COPOLYMER OF VINYL CHLORIDE AND VINYL ACETATE WHICH COMPRISES FROM 0.1 TO 10 PERCENT BY WEIGHT OF A COMPOUND CORRESPONDING TO THE FORMULA 